Cinnamyl carbamates

ABSTRACT

wherein ARYL is phenyl, substituted phenyl, naphthyl and substituted naphthyl in which said substituents are halogen, lower alkoxy, lower alkyl, or when ARYL is substituted phenyl the substituent is also 3,4-oriented-methylenedioxy; R and R1 are independently hydrogen, lower alkyl, chlorine or bromine; R2 is hydrogen, lower alkyl, or phenyl; and R3 and R4 are independently hydrogen, alkyl, lower alkenyl, carbethoxymethyl, phenyl and substituted phenyl in which said substituents are selected from the group halogen, lower alkoxy, lower alkyl and nitro, provided that only one of R3 or R4 is phenyl or substituted phenyl. The above-defined compounds are effective herbicides. Representative compounds are: cinnamyl-Nmethylcarbamate; 2-chlorocinnamyl-N-methylcarbamate; cinnamyl-Nallylcarbamate; cinnamyl carbamate; o-bromocinnamyl-N-methyl carbamate.   Compounds correspond to the formula

United 51 Fancher I CINNAMYL CARBAMATES Llewellyn W. Fancher. Orindu, Calif.

[75] Inventor:

[73} Assignee: Staulfer Chemical Company.

Wcstport. Conn.

Reissue of:

[64], Patent No.: 3,697,582

lssued: Oct. 10, 1972 Appl. No.: 719.700

Filed: Apr. 8, 1968 [52] U.S. Cl 260/482 C; 7l/70; 71/106;

7l/l l 1'. 263/3045; 260/463: 260/471 C [5 [1 Int. Cl. C07c 25/06 [58] Field of Search n 260/482 C [56] References Cited.

FOREIGN PATENTS OR APPLICATIONS 554.576 3/1958 Canada 260/482 837.7 l8 6/1960 United Kingdom. 260/482 374980 3/1964 Switzerland 260/482 (1.403.519 l0/1964 Netherlands........................260/482 Primary Examiner-Anton H. Sutto Assistant limmiuer-Paul J. Killos E Re. 28.496 Reissued July 29. 1975 Allows). Agar, or FirmHarry A. Pucini; Daniel C. Block; Edwin H. Baker [57] ABSTRACT Compounds correspond to the formula wherein ARYL is phenyl. substituted phenyl, nuphthyl and substituted naphthyl in which said suhstituents are halogen. lower ulkoxy. lower alkyl. or when ARYL is substituted phenyl the substituent is also 3,4-0rientedmethylenedioxy:

R and R are independently hydrogen. lower ulkyl,

chlorine or bromine; R is hydrogen. lower ulkyl. or

12 Claims. No Drawings CINNAMYL CARBAMATES Matter enclosed in heavy brackets I appears in the original patent but forms no part of this reissue specification: matter printed in italics indicates the additions made by reissue.

This invention relates to certain new compounds and their utility as active herbicidal substances. In particular. this invention pertains to certain novel cinnamyl carbamates corresponding to the general formula:

in which ARYL is selected from the group consisting of phenyl, naphthyl. substituted phenyl and substituted naphthyl in which said substituents are selected from the group consisting of halogen. lower alkoxy. lower alkyl. and provided that when ARYL is substituted phenyl the substituent is also 3.4-orientedmethylenedioxy; R and R are independently selected from the group consisting of hydrogen. lower alkyl. chlorine and bromine; R is selected from the group consisting of hydrogen. lower alkyl and phenyl; and R and R are independently selected from the group consisting of hydrogen. alkyl, lower alkenyl. carbethoxymethyl. phenyl and substituted phenyl in which said substituents are selected from the group halogen. lower alkoxy, lower alkyl and nitro. provided that only one of R or R is phenyl or substituted phenyl and further provided that when ARYL is phenyl. then R" or R is not phenyl. Among the active herbicidally effective compounds are included those compounds in which ARYL is phenyl and R or R is phenyl.

In the above description the following preferred embodiments are intended for the various groups; lower alkyl preferably includes those members which contain from one to about four carbon atoms, inclusive. in both straight chain and branched chain configurations. for example. methyl. ethyl. n-propyl, isopropyl. n-butyl. sec-butyl. and the like; lower alkoxy preferably includes those members which contain from one to about four carbon atoms. inclusive. in both straight chain and branched chain configurations, for example. methoxy, ethoxy. n-propoxy. isopropoxy. n-butoxy. sec-butoxy and the like; alkyl preferably includes those members which contain from one to about eight carbon atoms. inclusive. in both straight chain and branched chain configurations. for example. methyl. ethyl. n-propyl.

.isopropyl. n-butyl. sec-butyl. amyl. isoamyl. n-hexyl,

iso-hexyl. n-heptyl. n-octyl. iso-octyl and the like; lower alkenyl preferably includes those members of the group containing at least one double bond and containing from two to four carbon atoms, inclusive. for example. vinyl. allyl. propenyl. l-butenyl. Z-butenyl. 3-butenyl and the like: and the term halogen preferably includes fluorine. chlorine. bromine and iodine.

As a consequence of the special geometry of the carbon-carbon double bond and restricted rotation about this bond. the possibility exists in the compounds of the present invention of geometric isomcrism. Cis-trans isomerism is very frequently encountered in this type of structure containing a carbon-carbon double bond l: is recognized that the trans isomers are usually more stable than the corresponding cis isomers. The existence of both stereoisomeric forms is believed to exist for the majority of the compounds described herein. The compounds of the present invention are not limited to any specific geometric isomer configuration. In several instances. as seen below, both stereo isomers have been isolated and characterized. The physical properties of cis and trans isomers are usually quite similar and separation of both from a mixture by techniques such as fractional distillation or crystallization is not always possible.

The method of the present invention of controlling undesirable plants comprises applying an herbicidally effective amount ofthe above-described compounds to the area where control is desired. An herbicide is used herein to mean a compound which controls or modifies the growth of plants. By an herbicidally effective amount" is meant an amount of compound which causes a modifying effect upon the growth of plants.

Such modifying effects include all deviations from natural development. for example. killing. retardation. defoliation, desiccation. regulation. stunting. tillering. stimulation, dwarfing and the like. By "plants it is meant germinant seeds, emerging seedlings. and established vegetation including the roots and above-ground portions.

The compounds of the present invention can be pre pared by employing several different methods. in each method the appropriate cinnamyl alcohol is employed in a condensation reaction according to one of the following methods:'

in which ARYL. R. R. R. R and R are defined as above.

The intermediate cinnamyl-type alcohols are easily prepared according to the method taught in US. Pat. No. 3.094.56l. This method comprises the condensation of an appropriate arylaldehyde with acetaldehyde or homolog thereof in the presence of potassium hy- 3 droxide and ethanol to yield a cinnamaldchyde-type compound. This aldehyde is then reduced using aluminum iso-propoxide to form the cinnamyl alcohol-type compound. The reactions l l. (2) and {3a.b) proceed temperature remained below 55 C. The reaction is completed by refluxing the mixture for one hour. The bulk of the solvent is evaporated and the solid product crystallized from cyclohexane. There is obtained 96.2g.

readily in the liquid phase. The employment of a solof the title compound. m.p. 57-63+63C, The r vent is useful in facilitating processing as well as agitature is confirmed by infrared spectroscopy. tion of the reactants. Suitable solvents are benzene.

. chlorobenzene. toluene and the like. Where the reac- EXAMPLE tion employs an isocyanate. Equation (l) supra, it is Preparation of Cinnamyl-N.N-dimethyl-carbamate preferred to carry out the reaction in the presence of clnnamil alcohol g- -lZMl is dissolved in 25 a catalyst. such as. dibutyltindilaurate. When a basi cc. of pyridine. The mixture is cooled to 10 and halogen halide acceptor is preferred as the catalyst. as N.N-dimethyl-carbamyl chloride l5.l g. (0.14M) l3.4 in reactions (2) and (3a). supra. sodium carbonate or ml.) is added with stirring below 20 C. When the mix preferably tertiary amines. such as triethylamine. pyriture is warmed to 35 C.. a mild exothermic reaction dine. picoline and the like are chiefly employed. was evidenced y a telnpel'alure rise 10 The reaction temperatures are varied within a fairly heating on a steam bath for an additional 2.5 hours. the wide range. The process is carried out between 0 and mixture is allowed to stand at ambient temperature l80 C. preferably between about l0 C. and l00 C. overnight. The product is taken up in chloroform and Temperatures are maintained which allow operation in washed successively with water, cold dilute HCl and the liquid phase. again with water. The chloroform is dried over anhy- Compounds of the present invention are prepared by drous MgSO filtered and the chloroform removed in the following illustrative examples. vacuo. There is obtained 21 .4g. (87 per cent of theory) of a light colored liquid product. the title compound, EXAMPLE 1 n l.5482. The structure is confirmed by infrared Preparation of Cinnamyl-N-methylearbamate spectroscopy. I

Sixty-seven grams (0.5M) of cinnamyl alcohol is dis- The following is a table of the compounds which are solved in 100 ml. of benzene. To this solution is added prepared according to the procedures set forth above. 3 drops of dibutyl-tindilaurate and 30.2 g. (0.53M) Compound numbers have been assigned to them and (40.5 ml.) of methyliso-cyanate. The initial exothermic are employed for identification through the balance of reaction is controlled by heating or cooling so that the the specification:

' TABLE 1 R R R O R l l i ll Aryl-C=C-CHO-CN R4 Compound number Aryl R R R R R M.P.or n,,-"

l Phenyl H H H H Methyl 57-63C. 2 H H H H Ethyl 1.5450 3 H H H H Allyl V |.5510 4 H H H H p-Cl-phcnyl l07-l I01. 5 H H H H Phcnyl 1.6084 s H H H H n-Butyl Ms-48C. 7 H H Methyl H Methyl l.57tl7 8 H H H H o-CH O-phcnyl L595! 9 H Methyl H H Methyl Sir-6.1T. l0 H H H Plmiyl 754st l l H H H H p CH -phenyl S t-86C. l2 H Methyl H H Ethyl 1.562 l [3 H H Methyl H Phenyl l M192 [4 H H H Methyl Methyl 1.5482 l5 H H H Ethyl Ethyl 1.5232 l6 H H H Allyl Allyl 1.5159 17 'i' H H H H 2.5-Cl phenyl Ill-HT. l8 H H H H n-Octyl -181. 19 H H H H n-C H, 47-401. 20 H H H H i-C, H, 75-781. 2| H H H H -CH-:C(O)Ot (to-(0C. 22 H H H H m-NO,-phcnyl 92-95% 23 pCl-phcnyl H H H H Methyl lU5-lt)7C. 24 H H H H Sb-S 'C. 25 H H H Methyl 1.5671 26 Z.4Cl,-phcnyl H H H 1.5808 17 H H H H R-LXTC 18 3.4-Cl 8hcnyl H H H H IS-78C 29 3.4- l,- H H H Methyl ism 30 O-NO,-phenyl H H H H (la-sec. 3| H H H Methyl r5695 32 Phcnyl H H H H L548: .33" H H H Methyl -55U3 34 m-Cl-phcnyl H H H H 1 57-hlC. 35 Phcnyl H H H H H ll9-l ZlC. 36 o-Br-phcnyl j H H H H Methyl (m -67C. 37 3.4-mcthyll:ncdioxyphcnyl H H Methyl H L57 I 2 Jtl H H H Phcnyl LSWX) 9 H H Methyl Methyl L533} 40 Phony] H H H H K-CIH, [.5190 4| 4-CHfl0-phcnyl H H H H Methyl 84-86% 42 Z-CH;,O-phenyl H H H H 1545M TABLE l-Continued R R R'- 0 R" l l I ll Aryl-C=CCH-OCN RI Com pound number Aryl R R R" R R M.P.or mi" 4.1 I-CHD-phunyl H H H H L546) 44 2.6-Cl -phcnyl H H H H 45 J-CH -phunyI H H H H lUZ-IOPC'. 4n l-naphthyl H H H H L585} 47 Phcnyl H Bromine H H ll-4ST. 4x H H H Phenyl sit-93C. 49 Bromine H H H Methyl L549} 50 H H H Phenyl L5690 Sl o-cHr ht-n l H H H H Methyl .5450 52 m-Ch-phunyl H H Methyl H 1.5603 53 a-Cl-nuphthyl H H H Methyl 54 a-Br-naphthyl H H Methyl H 55 fl-CH O-naphthyl H H Methyl 56 B-n-C H- -O-naphthyl H Methyl H H 57 BCH naphthyl H Chlorine H Methyl 58 B-n-C.H-,-naphthyl Chlorine H H H 59 B-F-naphthyl Methyl H Ethyl Methyl 6O Phcnyl Chlorine n-C H, Phenyl H Allyl 6 I 4-n-C.H,O-phenyl Bromine H Methyl H Methyl 62 4-F-phenyl n-butyl H H H 63 4-l-phcnyl H Bromine H Methyl Ethyl 64 4-CH -phenyl Methyl H n-Butyl H nButyl 65 3.4-Cl phenyl n-Butyl H Phenyl H lsopropyl 66 o-NO- phenyl Chlorine H Methyl Allyl Allyl (Sis-isomer of Compound No. l. "Ck-isomer of Compound No. l-lv 'wat wlid.

Herbicidal Screening Tests on all seven weed species. It is the sum of the number of plus marks. so that an activity index of 21 represents As previously mentioned, the herein described comcomplete control of all seven weeds. The results of this pounds produced in the above-described manner are test are reported in Table ll. phytotoxic compounds which are usefuland valuable in Post-emergence herbicide test. Seeds of five weed controlling various plant species. Compounds of this species including hairy crabgrass, watergrass. Califorinvention are tested as herbicides in the following mannia r d 0315, Indian mustard, and curly dock and one ner. crop, pinto beans (Phaseolus vulgaris), are planted in Put-emergence herbicide test- On e ay P c g flats as described above for pre-emergerice screening. treatment. seeds of seven different weed species are Th fl t are placed in the greenhouse at 72-85F. and planted in individual rows using one species per row watered daily with a sprinkler. About 10 to 14 days BCI'OSS '16 Width of th: flat. The SCCdS USCd are hairy after planting when the primary leaves of the bean crabgl'ass (Dlgllana sangumall! P-)- YellQW plant are almost fully expanded and the first trifoliate fO tal (scw a B a rgr s leaves are just starting to form, the plants are sprayed. (Echinochloa crusgalh (L.) Beauv.), California red oat The spray is prepared by weighing out 50 mg. of the (Avena sativa (L-)). droot pigweed (Amaranthus retest compound, dissolving it in 5 ml. of acetone controflexu (L). In ia mustard (Br sica Jun ea (L-) taining 1% Tween 20 (polyoxy-ethylene sorbitan Coss.) and urly d k (Rum x lspus (L). Ampl monolaurate) and then addingSml. of water. The soluseeds are planted to g e about 0 O 0 ee ngs Pe tion is sprayed on the foliage using an atomizer. The rO te cmflg mfl. Pe g h e f he spray concentration is 0.5 percent and the rate would plants. The flats are watered after planting. The spraybe approximately 20 lb/acre if all of the spray were reing solution is prepared by dissolving 50 mg. of the test tained on the plant and the soil, but some spray is lost compound in 3 ml. of a solvent such as acetone conso it is estimated that the application rate is approxitaining l% Tween 20 (polyoxy-ethylene sorbitan mately l2.5 lb/acre. monolaurate). The following day each flat is sprayed at Beans are used to detect defoliants and plant growth the rate of 20 pounds of the candidate compound per regulators. The beans are trimmed to two or three 80 gallons of solution per acre. An atomizer is used to plants per flat by cutting off the excess weaker plants spray the solution on soil surface. The flats are placed several days before treatment. The treated plants are In a greenhouse at 80 F. and watered regularly. Two placed back in the greenhouse and care is taken to weeks later the degree of weed control is determined avoid sprinkling the treated foliage with water for three y comparing the umoumofgermmwon and o h f days after treatment. Water is appiled to the soil by each weed in the treated flats with weeds in several unmeans of a slow stream from a watering hose taking treated control flats. The rating system is as follows: care not to wet the foliage.

-= no significantinjury(0-l5 percent control) Injury rates are recorded 14 days after treatment. +=slight in ury (25-35 per cent control) The rating system is the same as described above for moderate injury (55-65 per cent control) the preemergence test where and +++-=severe injury or death l-l00 per cent control) An activity index is used to represent the total activity (+-H-) are used for the different rates of injury and control. The injury symptoms are also recorded. The maximum activity index for complete control of all the 7 species in the post-emergence screening test is l8 which represents the sum of the plus marks obtained with the six plant species used in the test. The herbicide activity index is shown in Table ll.

TABLE ll Hcrbicidal Activity Screening Results Herhicidal Activity index" Com- Pro-emergence PUSFLlllLfgt-HCL pound Number lZUlh/Al (I15 lb/Al l 21 lb 2 l5 l5 3 l4 lit 4 3 5 ll 9 6 l3 l3 7 0 ll 8 3 7 9 l5 l6 ll] 6 7 ll 6 l2 l2 6 l3 l3 5 l0 l4 3 l4 l5 l) 9 In 3 2 l7 0 4 l8 0 2 l9 lb I3 In It) 2! 3 l 22 0 3 23 l3 I2 24 ll 18 25 0 9 26 7 I5 27 8 I0 28 8 I0 2) l4 l8 30 3 l6 3! 0 9 32 l5 l? 33 6 7 34 l7 l8 35 l8 til 36 l9 l8 "El-K5401 control of all T weed species teamed pee-emergence. ill-Q5400"! control of all 6 weed species lesled post-emergence.

The compounds of the present invention are used as preemergence or post-emergence herbicides and are applied in a variety of ways at various concentrations. In practice. the compounds are formulated with an inert carrier. utilizing methods well-known to those skilled in the art. thereby making them suitable for ap plication as dusts. sprays. or drenches and the like in the form and manner required. The mixtures can be dispersed in water with the aid of a wetting agent or they can be employed in organic liquid compositions. oil and water. water in oil emulsions. with or without the addition of wetting, dispersing or emulsifying agents. The amount applied depends upon the nature of the seeds or plants to be controlled and the rate of application varies from l to approximately 50 pounds per-'acre. V

The phytotoxic compositions of this invention are applied to the plants in the conventional manner. Thus, the dust and liquid compositions can be applied to the plant by the use of power-clusters, boom and hand sprayers and spray-dusters. The compositions can also be applied from airplanes as a dust or a spray because they are effective in very low dosages. In order to modify or control growth of germinating seeds or emerging seedlings. as a typical example. the dust and liquid compositions are applied to the soil according to con ventional methods and are preferably distributed in the soil to a depth of at least flinch below the soil surface. It is not necessary that the phytotoxic compositions he admixed with the soil particles and these compositions can be applied merely by spraying the sprinkling the surface of the soil. The phytotoxic compositions of this invention can also be applied by addition to irrigation water supplied to the field to be treated. This method 7 of application permits the penetration of the compositions into the soil as the water is absorbed therein. Dust compositions. granular compositions or liquid formulations applied to the surface of the soil can he distrib uted below the surface of the coil by conventional means such as discing. dragging or mixing operations.

The phytotoxic compositions of this invention can also contain other additaments. for example fertilizers. pesticides and the like, used as adjuvants or in combination with any of the above-described adjuvants. Other phytotoxic compounds useful in combination with the above-described compounds include for example ZA-dichlorophenoxyacetic acids. 2.4.5-trichlorophenoxyacetic acid. 2-methyl-4-chlorophenoxyacetic acid and the salts. esters and amides thereof; triazine derivatives. such as 2,4-bist3-methoxypropylamino )-f methylthio-S-triazine; 2chloro-4eth vlamino--isopropylamino-S-triazine. and 2-ethylamino-4- isopropylamino-b-methylmercapto-S-triazine. urea derivatives. such as 3(3.4-dichlorophenyl)l.l-dimethyl urea and 3-(p-chlorophenyl)-l.l-dimethyl urea and acetamides such as N.N-diallyl-a-chloroacetamide, N- (a-chloroacetyl)hexamethylene imine. and N.N-diethyl-a-bromace-tamide, and the like: benzoic acids such as 3-amino-2,5-dichlorobenzoic. and; thiocarbamates. such as S-propyl dipropylthiocarbamate; S-ethyl-dipropylthiocarbamate, S-ethyl-cyclo hexylethyl-thiocarbamate. S-ethyl hexahydrol H-azepinel carbothioate and the like. Fertilizers useful in combina tion with the active ingredients include for example ammonium nitrate. urea and superphosphate. Other useful additaments include materials in which plant orgahisms take root and grow such as compost. manure. humus. sand and the like.'

The concentration of a compound of the present invention. constituting an effective amount in the best mode of administration in the utility disclosed is readily determinable by those skilled in the art. Various changes and modifications are possible without departing from the spirit and scope of the invention described herein and will be apparent to those skilled in the art to which it pertains. It is accordingly intended that the present invention shall only be limited by the scope of the claims.

What is claimed is:

[1. A compound having the formula wherein ARYL is selected from the group consisting of phenyl. nuphthyl. substituted phenyl and substituted naphthyl in which said substituents are selected from the group consisting of halogen. lower alkoity. lower alkyl. and provided that when ARYL is substituted phenyl the substituent is also 3.4-oriented methylenedioxy;

R and R' are independently selected from the group consisting of hydrogen. lower alkyl, chlorine and bromine;

R is selected from the group consisting of hydrogen.

lower alkyl and phenyl; and

R and R are independently selected from the group consisting of hydrogen. alkyl. lower ulkenyl. curbethoxymethyl. phenyl and substituted phenyl in which said substituents are selected from the group halogen. lower alkoxy. lower alkyl and nitro; provided that only one of R or R is phenyl or substituted phenyl; and further provided that when ARYL is phenyl then R or R is not phenyl.]

2. A compound [of claim 1] having the flH'IPHl/G in which ARYL is mono-halophenyL R and R, R and R are each hydrogen, an R is,alky1.

3. A compound ofclaim 2 in which mono-halophenyl is o-chlorophenyl and R is methyl.

4. A compound of claim Z'i'n which mono halophenyl is p-chlorophenyl and R is methyl.

5. A compound ofclaim 2 in which mono-halophenyl is m-chlorophenyl and R is methyl.

6. A compound of claim 2 in which mono-halophenyl is o-bromophenyl and R is methyl.

[7. A compound of claim I in which ARYL is phenyl. R. R, R and R are each hydrogen, and R is a1- k l.]

[8. A compound ofclaim 7 in which R is methyl] [9. A compound of claim 7 in which R is ethyl] I: 10. A compound of claim 7 in which R is nbutyL] [11. A compound of claim 7 in which R is noctyl.] [12. A compound of claim 7 in which R is np w -II [13. A compound of claim 7 in which R is ipropylJ [14. A compound ofclaim 1 in which ARYL is phe nyl and R. R. R R and R are each hydrogen] 15. A compound [of claim 1] having the formula in which ARYL is mono-halophenyl. [R. R and R are each hydrogen] R" and R are each alkyl.

16. A compound of claim 15 in which ARYL is ochlorophenyl. R and R are each methyl.

17. A compound [of claim 1] having the formula in which ARYL is phenyl. [R. R and R are each hyin which ARYL is phenyl R, R. R and R are each hydrogen,] and R is lower alkenyl.

21. A compound of claim 20 in which R is ally-l.

* i t i i 

2. A compound (of claim 1) having the formula
 3. A compound of claim 2 in which mono-halophenyl is o-chlorophenyl and R4 is methyl.
 4. A compound of claim 2 in which mono-halophenyl is p-chlorophenyl and R4 is methyl.
 5. A compound of claim 2 in which mono-halophenyl is m-chlorophenyl and R4 is methyl.
 6. A compound of claim 2 in which mono-halophenyl is o-bromophenyl and R4 is methyl.
 15. A compound (of claim 1) having the formula
 16. A compound of claim 15 in which ARYL is o-chlorophenyl, R3 and R4 are each methyl.
 17. A compound (of claim 1) having the formula
 18. A compound of claim 17 in which R3 and R4 are each methyl.
 19. A compound of claim 17 in which R3 and R4 are each ethyl.
 20. A compound (of claim 1) having the formula
 21. A compound of claim 20 in which R4 is allyl. 